Sulfosuccinate derivatives as detergent builders

ABSTRACT

Novel salts of Alpha -substituted- Beta -sulfosuccinic acids having the general formula:   wherein R is hydrogen or an organic moiety, Z is selected from the group consisting of O, S, SO, SO2, N and NO and M is an alkali metal, ammonium or substituted ammonium cations, useful as detergents and/or detergent builders and detergent compositions containing same.

United States Patent [191 Lamberti Dec. 9, 1975 SULFOSUCCINATEDERIVATIVES AS DETERGENT BUILDERS [75] Inventor: Vincent Lamberti, UpperSaddle River, NJ.

[73] Assignee: Lever Brothers Company, New

York, N .Y.

[22] Filed: Sept. 5, 1973 [21] Appl. No: 394,613

Related 1.1.8. Application Data [62] Division of Ser No. 156933. June25, 1971.

abandoned.

[52] US. Cl. 260/247.1 E; 260/501.l2; 260/501.l5; 260/501.l9;260/501.2l; 260/513 R;

[51] Int. Cl. C07D 295/00; CO'IC 143/00 [58] Field of Search 260/513 R,513 B, 501.21, 260/501.l5, 501.19, 247.1 E

[56) References Cited UNITED STATES PATENTS 3,635,829 1/1972 Yang252/526 3,706,771 12/1972 Kremers et a1. 260/3468 OTHER PUBLICATIONSBeilstein, Handbuch Der Org. Chem." Band 4, pp. 72,75 (1962),

Primary Examiner-James O. Thomas, Jr. Assistant ExaminerNicky ChanAttorney, Agent, or FirmArnold Grant. Esq.

[57] ABSTRACT Novel salts of a-substituted/3sulfosuccinic acids havingthe general formula:

7 Claims, N0 Drawings SULFOSUCCINATE DERIVATIVES AS DETERGENT BUILDERSThis is a division of application Ser. No. 156,933, filed June 25, 197i,now abandoned.

BACKGROUND OF THE INVENTION Eutrophication is the process of excessivefertilization of aquatic plants through enrichment of waters withnutrients, such as carbon, nitrogen, phosphorus, potassium, iron, tracemetals and vitamins.

Although there is no present adequate proof, it has been postulated thatthe phosphorus-containing builders present in detergent compositions canbe a factor in eutrophication. Therefore any substitutes which do notcontain phosphorus may decrease to some extent the eutrophication.

It is therefore an object of the present invention to provide novelcompounds which are useful as detergent builders. It is another objectof the present invention to provide novel compounds which function assurface active agents and as detergent builders. It is still anotherobject of the present invention to provide detergent compositions whichare free of phosphorus-containing builders such as the alkali metalcondensed phosphates.

DESCRIPTION OF THE INVENTION It has now been discovered that the alkalimetal ammonium and substituted ammonium salts of certain sulfoaliphaticdicarboxylic acids can serve as effective de tergent builders indetergent compositions. The detergent builders and their acid formsemployed in accordance with one embodiment of the present invention canbe generally described as a-substituted-B-sulfosuccinic acids and saltsthereof having the general formula:

COOH COOH wherein Z is selected from the group consisting of O, 5, SOand S R is selected from the group consisting of hydrogen, alkylcontaining [-30 carbon atoms, phenyl, carboxyl substituted and monodiortri-alkyl substituted phenyl, wherein the alkyl group or groups contain1-4 carbon atoms; sulfoand carboxy-alkyl, wherein the alkyl moietycontains 1-4 carbon atoms", and R'Z(CH CH O)nCH CH wherein R is H oralkyl containing l24 carbon atoms; Z is as above; and n is 0 or aninteger of from 1-1 5 and the alkali metal, ammonium and substitutedammonium salts thereof.

Thus, specific compounds and classes of compounds embraced by thegeneric formula above include:

a-hydroxy-B-sulfosuccinic acids a-alkoxy-B-sulfosuccinic acidsa-phenoxy-B-sulfosuccinic acids a-carboxyphenoxy-B-sulfosuccinic acidsa-alkylphenoxy-B-sulfosuccinic acids a-carboxyalkoxy-B-sulfosuccinicacids a-sulfoalkoxy-B-sulfosuccinic acids a-alkoxyethoxy-B-sulfosuccinicacids a-alkoxypolyethyleneoxyethoxy-fi-sulfosuccinic acidsa-hydroxyalkoxy-fi-sulfosuccinic acids; the alkali metal, ammonium andsubstituted ammonium salts thereof; and the thio, sulfinyl and sulfonylanalogs of all the foregoing compounds wherein the oxygen group attachedto the a-carbon of the succinic acid or succinate moiety is replaced byS, SO- or SO respectively, and/or wherein the cases of theoz-alkoxyethoxy compounds and the a-alkoxypolyethyieneoxyethoxycompounds the oxygen attached to the alkyl group (R') is replaced by S,SO-- or SO In accordance with another embodiment of the presentinvention are the nitrogen containing a-substitutedfi-sulfosuccinicacids and salts thereof having the following general formula:

, OOH COOH wherein at least one of R and R is hydrogen, C to C alkyl, C,to C hydroxyalkyl, carboxymethyl, carboxyethyl, sulfomethyl andsulfoethyl, or R and R may be joined to form a morpholinyl moiety; withthe proviso that both R, and R may not at the same time be hydrogen.

Thus, broadly the compounds of Formula I differ from the compounds ofFormula I] only in the atom represented by Z.

Representative compounds and classes of compounds embraced by genericFormula II above include:

a-alkylamino-B-sulfosuccinic acids such as amethylamino, a-propylamino,oz-octylamino and 0:- laurylamino-B-sulfosuccinic acid;

a-dialkylamino-B-sulfosuccinic acids such as a-dimethylarnino,a-ethylmethylamino, a-methylhexylamino anda-dioctylamino-B-sulfosuccinic acid;

a-hydroxyalkyl-B-sulfosuccinic acids such as ahydroxyethylamino,a-hydroxybutylamino and oz-bis(- hydroxyethyl )amino-B-sulfosuccinicacid;

a-carboxyalkylamino-B-sulfosuccinic acids such as a-carboxymethylamino,a-carboxyethylamino-B-sulfosuccinic acid and the corresponding sulfoanalogs;

a-morpholinyl-B-sulfosuccinic acid; and the mono or poly salts thereof.

In accordance with still another embodiment of the present invention arethe amine oxide derivatives of Formula II, wherein the nitrogen is atertiary atom, corresponding to the following general formula:

Formula lll wherein R. and R, are as is designated in Formula II withthe proviso that neither R, nor R, can be hydrogen.

As will be appreciated by those skilled in the art, the compounds of theinvention contain at least two asymmetric carbon atoms and therefore canexist in several optically active forms as well as optically inactivemixtures (racemates). For purposes of this invention, the compounds asdefined are intended to include all of the stereoisomeric forms andmixtures thereof.

In addition to the detergent building properties exhibited by the entireclass of compounds described above, certain select members also exhibitproperties which make them useful as wetting and foaming agents and thusconstitute a class of novel surface active agents. For example, thea-alkoxy-B-sulfosuccinic acids and the thio analogs, containing fromabout 1-8 carbons, preferably from about l to about 4 carbon atoms,exhibit excellent detergent building properties whereas the higherhomologs containing from about 9-30 and more preferably 924 carbon atomsin the alkyl chain, additionally exhibit wetting, foaming and detergencyproperties.

Similarly, the a-alkoxyethoxy anda-alkoxypolyethyleneoxyethoxy-Bsulfosuccinic acid compounds containingfrom about 930 and preferably about 9-24 carbon atoms in the alkoxymoiety are also useful as wetting agents, foaming agents and detergentsas well as detergent builders.

Although the builders of the present invention may be utilized as thefree acid provided sufficient alkaline additives are included in thedetergent composition to convert the acid forms in situ to the normalsalt forms, that alkali metal, ammonium and substituted ammo nium saltsof the a-substituted-B-sulfosuccinic acids are preferred. Included inthe substituted ammonium salts that can be employed are themonoethanolammonium, diethanolammonium, triethanolammonium,methylammonium, dimethylammonium, trimethylammonium,tetramethylammonium, morpholinium, N-methylmonoethanolammonium andN-ethylmonoethanolammonium salts and mixtures thereof.

The utility of the compounds of the present invention is not onlyreflected in terms of excellent building and biodegradability propertiesbut also in low cost of preparation, since they are prepared fromreadily available and inexpensive materials. For example, the compoundscontemplated in this invention are derived from sulfomaleic anhydrideand readily available alcohols, thiols, hydroxy acids and amines.

More specifically, the compounds contemplated in this invention arereaction products derived at least in part from sulfomaleic acid orsulfomaleic acid with compounds having an active hydrogen atom.

Compounds having an active hydrogen and suitable for use in preparingthe builders of the present invention are monodior polyhydric alcoholsand monodi or polyhydroxy acids and their sulfur-containing analogs.Suitable examples of the aforementioned monohydric alcohols includealkoxyalkanols such as methoxyethanol and the linear primary andsecondary alcohols containing up to 30 carbon atoms and their thioanalogs; aromatic alcohols particularly the carbocyclic monoand bicyclicaromatic alcohols. such as naphthols and phenols and the monodior tri- C-C, alkyl ring substituted derivatives thereof. Suitable examples ofdihydric alcohols include the glycols such as ethylene glycol. propyleneglycol. butylene glycol. trimethylene glycol, tctramethylene glycol.pentamethylene glycol, hexamethylcne glycol. hcptamethylene glycol, longchain l,2-diols containing from 8-30 carbon atoms and aromaticcarbocyclic glycols such as phenylethylene glycol. Similarly. suitablepolyhydric alcohols include glycerol, pentaerythritol. hexanetriol.sugars and their thio analogs.

in addition to the alcohols. the hydroxy carboxylic and sulfonic acids(in their ester and acid/salt forms, respectively) may also react withsulfomaleic anhydride and sulfomaleic acid. These include glycollic,lactic, glyceric. hydroxypropionic, salicyclic and mer capto aceticacid, hydroxymethanesulfonic acid and hydroxyethanesulfonic acid.

Still another important class of compounds containing active hydrogensare ethylene oxide adducts of C, to C primary and secondary alcoholswith 1-1 5 moles of ethylene oxide.

In general, the a-substituted-B-sulfosuccinate salts, wherein theasubstituent is joined to the a-carbon atom of the sulfosuccinate moietyby an O or S linkage, may be prepared by heating at a temperature offrom about 25 to 120C, and preferably 60 to 100C, sulfomaleic anhydridewith a compound having an active hydrogen followed by further treatmentwith an alkali metal hydroxide. The desired a-oxy ora-thio-B-sulfosuccinate may then be recovered and purified usingconventional techniques.

The a-substituted-B-sulfosuccinate salts wherein the a-substituent isjoined to the a-carbon atom of the sulfosuccinate moiety by an S0 or S0linkage may be prepared by treating the appropriate a-substituted thio-B-sulfosuccinate with hydrogen peroxide according to the methodsdescribed on pages 471472 in the text, Reagents for Organic Synthesis"by Fieser and Fieser, published by John Wiley & Sons, Inc., 1967,incorporated by reference herein.

The a-substituted-B-sulfosuccinate salts wherein the a-substituent isjoined to the a-carbon atom of the sulfosuccinate moiety by an aminofunction (Formula ll) may be prepared by reacting an appropriatelysubstituted or unsubstituted primary or secondary amine with alkalimetal salts of sulfomaleic acid. Typical amines suitable for reaction toform the a-substituted amino-B-sulfosuccinates include:

ethanolamine diethanolamine propanolamine morpholineN-methylethanolamine glycine alanine N-methyl taurine alkylaminescontaining l-2O carbons in the alkyl chain, as well as other amineshaving a replaceable or active hydrogen and a basicity comparable to theaforementioned amines.

In particular the a-amino substituted-B-sulfosuccinates derived fromwater-soluble amines may be prepared by reacting in aqueous solutionwithout the aid of heat and those derived from water-insoluble amines(i.e.. higher alkylamines) are reacted in a mixed solvent system such asethanol/water or dioxane/water at temperaturcs ranging from about 25 toabout C; isolation from the reaction medium, and purification ifdesired, being effected by conventional methods.

The compounds of Formula lll may be prepared by reacting the tertiaryamine compounds of Formula [I with oxidizing agents such as hydrogenperoxide, peroxyacetic and peroxyformic acid in the manner described foroxidizing tertiary amines by Hoh et al., J. Am. Oil Chemists Soc., 40,268 (I963).

In preparing the sulfosuccinate salts from the free acid, the amount ofbase utilized will determine whether the monodior tri-salt is obtained.For example, the use of one mole of base (i.e., sodium hydroxide) permole of a-hydroxy-B-sulfosuccinic acid yields the monosodium salt; theuse of two moles of sodium hydroxide, the disodium salt and the use ofthree moles of sodium hydroxide. the trisodium salt. When R iscarboxymethyl, carboxyethyl, sulfomethyl or sulfoethyl, a tetrasalt canalso be obtained. Similarly, other bases,

S such as ammonium hydroxide and organic amines, may be utilized in thesame manner to afford the type of salt desired.

According to the present invention, excellent cleaning results can beobtained by using the builders described above with a wide range ofdetergent surface active materials and mixtures thereof in any of theusual physical forms for such compositions such as powders, beads,flakes, bars, tablets, noodles, liquids and the like. The builders canbe used singularly, in combination with each other as the sole builderin the detergent composition or in combination with other well-knowndetergent builders such as sodium nitrilotriacetate, sodiumethylenediaminetetraacetate, sodium tripolyphosphate, trisodiumorthophosphate, sodium and potassium pyrophosphate, sodium polyacrylate,disodium oxydiacetate, trisodium citrate, trisodiumcarboxymethyloxysuccinate, salts of oxidized starches and sodium orpotassium carbonate, as well as other conventional organic and inorganicbuilders.

When using the detergent compositions of the invention to wash clothes,the wash solutions should have a pH from about 7 to l2 and preferablyfrom about 9 to l 1 throughout the washing cycle. Therefore, thepresence of an alkaline buffer in the detergent composition is usuallydesirable particularly when the soil to be removed from the clothes hasa high content of acidic components. Suitable buffers include any of thecommon organic and/or inorganic buffers such as monoethanolamine,diethanolamine, triethanolamine, sodium and potassium silicates, sodiumand potassium carbonates and bicarbonates and the like.

In the detergent compositions of the present invention, the onlyessential ingredients are the detergent surface active material and thebuilder. The weight percent of the builder present in the detergentcomposition will range from about to about 90% and preferably from about20 to about 60% and more preferably 35-50% by weight of the total weightof the composition. When expressed as a weight ratio of builder tosurfactant, the builders used in the instant invention will generally bepresent in a ratio of about 1:10 to about HM, and preferably 2:1 to 5:ldepending on the end use or whether a heavy-duty or light-duty detergentis desired. When the builders are used in mechanical dishwashingcompositions, the ratio of builder to surfactant is from about :1 toabout 50:l.

The detergent surface active compounds which can be used within thecompositions of this invention include anionic, nonionic, zwitterionic,ampholytic detergent compounds and mixtures thereof. These suitablesubstances are outlined at length below.

a. Anionic detergent compositions which can be used in the compositionsof this invention include both soap and non-soap detergent compounds.Examples of suitable soaps are the sodium, potassium, ammonium andalkylolammonium salts of higher fatty acids (C C Particularly useful arethe sodium or potassium salts of the mixtures of fatty acids derivedfrom coconut oil and tallow, i.e., sodium or potassium tallow andcoconut soap and tall oil. Examples of anionic organic non-soapdetergent compounds are the water soluble salts, alkali metal salts oforganic sulfuric reaction products having in their molecular structurean alkyl radical containing from about 8 to about 22 carbon atoms and aradical selected from the group consisting of sulfonic acid and sulfuricacid ester radicals. Important examples of the synthetic detergentswhich form a part of the compositions of the present invention are thesodium or potassium alkyl sulfates especially those obtained bysulfating the higher alcohols (Cg-C13 carbon atoms) produced by reducingthe glycerides of tallow or coconut oil; sodium or potassium alkylbenzensulfonates in which the alkyl group contains from about 9 to about20 carbon atoms and in which the alkyl group is attached to the benzenering in either the one position or at the secondary positions such as inLAS,* sodium p- (2-dodecyl-)benzenesulfonate, sodium p-(2-octadecyl)benzenesulfonates and sodium p-(3- dodecyl)benzenesulfonate;sodium slkyl glyceryl ether sulfonates, especially those ethers of thehigher alcohols derived from tallow coconut oil and synthetic alcoholsderived from petroleum; sodium coconut oil fatty acid monoglyceridesulfates and sulfonates, sodium or potassium salts of sulfuric acidesters and carboxymethylated derivatives of. the reaction product of onemole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols)and about 1 to 6 moles of ethylene oxide per molecule and in which thealkyl radicals contain about 9 to about 18 carbon atoms; the reactionproduct of fatty acids esterified with isethionic acid and neutralizedwith sodium hydroxide where, for example, the fatty acids are derivedfrom coconut oil; sodium or potassium salts of fatty acid amides ofmethyl taurine in which the fatty acids, for example, are derived fromcoconut; alkane sulfonates such as those derived by reactingalpha-olefins containing 8 to 20 carbon atoms with sodium bisulfite andthose derived by reacting paraftins with S0 and Cl and then hydrolyzingwith a base to produce a random sulfonate; alpha-olefin sulfonates suchas those derived by reacting alpha-olefins with 50;, and thenneutralizing the reaction product; and

others known in the art. *Sodium linear secondar alkyl (C -C benzenesulfonate.

b. Nonionic synthetic detergents may be broadly defined as compoundswhich do not ionize in water solution. For example, a well-known classof nonionic synthetic detergents is made available on the market underthe trade name of Pluronic." These compounds are formed by condensingethylene oxide with an hydrophobic base formed by the condensation ofpropylene oxide with propylene glycol. The hydrophobic portion of themolecule which, of course, exhibits water insolubility has a molecularweight of from about 1,500 to L800. The addition of polyoxyethyleneradicals to this hydrophobic portion tends to increase the watersolubility of the molecule as a whole and the liquid character of theproduct is retained up to the point where polyoxyethylene content isabout SO /r of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

I The polyethylene oxide condensates of alkylphenols, e.g., thecondensation products of alkylphenols having an alkyl group containingfrom about 6 to l2 carbon atoms in either a straight chain or branchedchain configuration, with ethylene oxide, the said ethylene oxide beingpresent in amounts equal to 5 to 25 moles of ethylene oxide per mole ofalkylphenols. The alkyl substituent in such compounds may be derivedfrom polymerized propylene, disobutylene, octene, dodecene. or nonene,for example.

2. Those derived from the condensation of ethylene oxide with theproduct resulting from the reaction of propylene oxide andethylenediamine. For example, compounds containing from about 40 toabout polyoxyethylene by weight and having a molecular weight of fromabout 5,000 to about I L000 resulting from the reaction of ethyleneoxide groups with a hydrophobic base constituted of the reaction productof ethylene diamine and excess propylene oxide, said hydrophobic basehaving a molecular weight of the order of 2.500 to 3,000 aresatisfactory.

3. The condensation product of aliphatic alcohols, primary or secondary,having from 8 to 18 carbon atoms, in either straight chain or branchedconfiguration, with ethylene oxide, e.g., a coconut alcohol-ethyleneoxide condensate having from 6 to 30 moles of ethylene oxide per mole ofcoconut alcohol, the coconut alcohol fraction having from ID to l4carbon atoms; a C ,,C,,, random secondary alcohol derived fromn-paraffins and condensed with 7 moles of ethylene oxide per mole ofsecondary alcohol.

4. Long chain tertiary amine oxides corresponding to the followinggeneral formula, R,R R N- O, wherein R is an alkyl radical of from about8 to 18 carbon atoms and R and R are each methyl, ethyl or hydroxy ethylradicals. The arrow in the formula is a conventional representation of asemi-polar bond. Examples of amine oxides suitable for use in thisinvention include dimethyloctylamine oxide, dimethyldecylamine oxide,dimethyldodecylamine oxide, dimethyltetradecylamine oxide anddimethylhexadecylamine oxide, N-bis(hydroxyethyl)dodecylamine oxide.

5. Long chain tertiary phosphine oxides corresponding to the followingformula RR'R"P O, wherein R is an alkyl, alkenyl or monohydroxyalkylradical ranging from 10 to l8 carbon atoms in chain length and R and R"are each alkyl or monohydroxyalkyl groups containing from I to 3 carbonatoms. The arrow in the formula is a conventional representation of asemipolar bond. Examples of suitable phosphine oxides are:

dimethyldodecylphosphine oxide,

dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide,cetyldimethylphosphine oxide, dimethylstearylphosphine oxide,cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide,diethyltetradecylphosphine oxide,

bis( hydroxymethyl )dodecylphosphine oxide,

bis( 2-hydroxyethyl )dodecylphosphine oxide,

2-hydroxypropylmethyltetradecylphosphine oxide,

dimethyloleylphosphine oxide, and dimethyl-Z-hydroxydodecylphosphineoxide.

6, Dialkyl sulfoxides corresponding to the following formula, RR'S O,wherein R is an alkyl, alkenyl, betaor gamma-monohydroxyalkyl radical oran alkyl or betaor gamma-monohydroxyalkyl radical containing one or twoother oxygen atoms in the chain, the R groups ranging from l0 to 18carbon atoms in chain length, and wherein R is methyl, ethyl or alkylol.Examples of suitable sulfoxide compounds are:

dodecyl methyl sulfoxide tetradecyl methyl sulfoxide 3-hydroxytridecylmethyl sulfoxide Z-hydroxydodecyl methyl sulfoxide3-hydroxy'4-decyloxybutyl methyl sulfoxide 3-hydroxy-4-dodecylcoxybutylmethyl sulfoxide 2-hydroxy-3-decyloxypropyl methyl sulfoxideZ-hydroxy-3-dodecyloxypropyl methyl sulfoxide dodecyl ethyl sulfoxideZ-hydroxydodecyl ethyl sulfoxide dodecyl-2-hydroxy ethyl sulfoxide c.Ampholytic synthetic detergents can be broadly described as derivativesof aliphatic secondary and tertiary amines, in which the aliphaticradical may be straight chain or branched and wherein one of thealiphatic substituents contains from about 8 to l8 carbon atoms and onecontains an anionic water solubilizing group. Examples of compoundsfalling within this definition are sodium-3-dodecylaminopropionate andsodium-3-dodecylaminopropanesulfonate and sodium N-2-hydroxydodecyl-N-methyl-taurate.

d. Zwitterionic synthetic detergents can be broadly described asderivatives of aliphatic quaternary ammonium compounds, sulfoniumcompounds and phosphonium compounds in which the aliphatic radical maybe straight chain or branched and wherein one of the aliphaticsubstituents contains from about 8 to 18 carbon atoms and one containsan anionic water solubilizing group. Examples of compounds fallingwithin this definition are 3-(N,Ndimethyl-Nhexadecylammonio)propanel-sulfonatc, 3-(N,N-dimethylN-hexadecylammonio)-2-hydroxypropane-l-sulfonate,3-(dodecylmethylsulfonium) propane sulfonate, and3-(cetylmethylphosphonium)ethane sulfonate.

Other materials which may be present in the detergent compositions ofthe invention in generally minor amounts are those conventionallypresent therein. Typ ical examples thereof include the well-knownsoil-suspending agents, hydrotropes, corrosion inhibitors, dyes,perfumes, fillers such as sodium sulfate, optical brighteners,perborates, bleaches, bleach activators, enzymes, suds boosters, sudsdepressants, germicides, fungicides, anti-tamishing agents, cationicdetergents, fabric softening agents and in the case of liquidcompositions, opacifiers and organic solvents. The balance of thedetergent compositions may be water or inert filler.

It has been discovered that when higher than normal levels of anionic,nonionic, ampholytic or zwitterionic surfactants are used with thesulfosuccinate derivative salts of this invention, the detergency of theformulation is significantly enhanced particularly at low formulationconcentration (-0. 1%) which are typically used by the US. housewife.For enhanced results the detergent formulation should contain surfactantlevels of about 25 to about 45% by weight and the sulfosuccinatederivative salt levels of about 25 to about by weight in the cases wherethe surfactants are anionic, ampholytic or zwitterionic. When thesurfactant is a nonionic, enhanced detergency results are obtained whenthe level of said nonionic in the formulation is from about l5 to 30% byweight and the level of sulfosuccinate derivative salt is from about 25to about by weight.

in addition to their use in general household detergent compositions,the builders of the present invention find utility as boiler scaleremovers, stain removers and general chelating agents. When used at pHsof about 2 to about 5 as partially neutralized alkali metal, ammonium orsubstituted ammonium salts, especially in combination with wettingagents and surfactants, the compounds of the invention are excellentmetal cleaning compounds.

Table 1 further illustrates the present invention. The detergentformulations set forth in the Table represent detergent compositionscontaining the builders of the present invention in combination withrepresentative classes of surface active agents compared with control orstandard phosphate built detergent compositions. The compositions wereprepared by blending together the recited components in the proportionsindicated, including an anticorrosive agent and buffer agent (so diumsilicate). The compositions were then tested on vacuum cleaner dustsoiled cloth for detergency or cleaning ability in the Terg-O-Tometertest; wherein washing conditions are as indicated and the resultsreported as detergency units. The average detergency units (DU) of theformulation is the final reflectance value of the washed cloth (averageof 2 runs) minus the initial reflectance of the soiled cloth, thereflectances being obtained by measurement with a Gardner automaticcolor difference meter, Model AC-3.

cated that all of the sulfomaleic acid had hydrated within the firsthour of reflux. The reaction mixture was then passed through a column ofcation exchange resin. A portion of the effluent was then neutralized topH 8.5 and evaporated to a white crystalline residue l9.2 gm), whichcontained 80.9% of trisodium a-hydroxy-B- sulfosuccinate as determinedby NMR analysis (using D solvent and K biphthalate as an internalstandard) and 10.4% water by Karl Fischer analysis.

EXAMPLE 2 a-Thiosubstituted-BSulfosuccinates TABLE 1 ComponentComposition adodccyloxy" cr-methoxy" acarboxymethoxy" a-dodecyloxyethoxya-dodecylthio" Na l o Sodium silicate (SiO :Na O

2.4:] Anionic Anionic Nonionic Ampholytic" Zwitterionic' WaterFormulation Detergency (DU 's) 2 &

Component ol-hydroxy a( 2hydroxy ethoxy a-dodecyloxy" a-methoxy"a-carboxymethoxy mdodecyloxyethoxy" a-dodecylthio" Na P O Sodiumsilicate (SiO :Na,O 2.4:]

Anionic Anionic Nonionic Ampholytic' Zwitterionic' Water FormulationConcentration Detergency (DUs) "Sodium salts ofa-suhstitutcd-B-sulfosuccinate Sodium linear secondary alltyl (Cw-Cm)benzene sulfonate Controls Composition) "C C linear secondary alcoholscthoxyluted with 7 moles ethylene oxide/mole alcohol "C -C HAMT (sodiumhydroxyalkyl N-rnethyl taumte) 'Sulfohetaine DCH(cododimcthylsulfopropyl betaine) S7 Washing conditions I80 ppm (2:lCaVMg); 120F: pH 10 EXAMPLE 1 Preparation of Trisodiuma-Hydroxy-B-Sulfosuccinate Sulfomaleic anhydride was prepared by heatinga (,0

mixture of 1 mole of sulfur trioxide with 1 mole of maleic anhydridefirst at 60C until the exothermic reaction subsided and then at l001 10Cfor 3 hours. Forty-five gm of sulfomaleic anhydride product was thenmixed with gm of ice and the resulting solution ex- ,5

tracted 25 times with ml portions of ether to remove maleic acid. A 20ml portion of the resulting aqueous phase was collected, adjusted to pHl l with calcium hydroxide and refluxed for 4 hours. NMR analysisinditrisodium a-ethylthio-B-sulfosuccinate' EXAMPLE 3 Preparation ofTrisodium a-Methoxy-B-Sulfosuccinate Sulfomaleic anhydride, 3.9 gm, wasdissolved in 25 ml of methanol and refluxed for hours. Then, 24 gm of25% sodium methoxide in methanol was added and the solution was refluxedfor 2 hours. The methanol was then evaporated and the residue wasdissolved in 100 ml of water and heated for 1 hour at 80C. The solutionwas then decolorized with 5 gm of charcoal, filtered and evaporated. Thecrude residue of trisodium a-methoxy-B-sulfosuccinate was purified bytrituration with acetic acid and then filtered, washed with acetone anddried.

a-ethoxy-B-sulfosuccinate may be prepared by substituting ethanol andsodium ethoxide in the procedure described above.

EXAMPLE 4 Preparation of Trisodium a-Dodecyloxy-B- SulfosuccinateSulfomaleic anhydride gm) are mixed with 80 gm (0.45 mole) ofn-dodecanol and heated at 100C for 14 hours. A solution of 7.04 gm ofsodium hydroxide in 50 ml water is then added and the mixture heated at60C for 2 hours. The heated mixture is then extracted three times with300 cc portions of acetone (at reflux) and the acetone insolublefraction is then filtered, washed with additional acetone and dried togive 16.2 gm of the title compound (structure confirmed by NMR and ionexchange of a sample followed by titration with standard sodiumhydroxide: neutralization equivalent: found 147.0, theory l49.3).

EXAMPLE 5 Preparation of Trisodium a-Doclecyloxyethoxy-B-SulfosuccinateUsing the procedure of Example 4 and substituting 37 gm (0.32 mole) of2-dodecyloxyethanol in place of the n-dodecanol there is obtainedtrisodium adodecyloxyethoxy-/3-sulfosuccinate.

EXAMPLES 6-8 Using n-tetradecanol in place of n-dodecanol in theprocedure of Example 4 and carrying out the hydrolysis step with 10%excess aqueous sodium hydroxide at 80C for 4 hours instead of 60C at 2hours, there is obtained trisodium a-tetradecyloxy-B-sulfosuccinate(Example 6). Similarly, using n-hexadecanol in place of n dodecanol,there is obtained trisodium a-hexadecycloxy-B-sulfosuccinate (Example7); using noctadecanol, there is obtained trisodiumaoctadecyloxy-B-sulfosuccinate (Example 8).

EXAMPLE 9 Preparation of Trisodium a-Hydroxyethoxy-B-SulfosuccinateSulfomaleic anhydride gm) is mixed with 37.2 gm (0.6 mole) of ethyleneglycol and heated at 80C for 4 hours. A solution of 16 gm (0.4 mole) ofsodium hydroxide in ml of water is then added and the mixture heated atC for 4 hours. The mixture is then mixed with acetone to precipitatetrisodium a-hydroxyethoxy-B-sulfosuccinate, which is purified byrepeated extractions with hot acetone to remove all ethylene glycol andwater followed by filtration and drying in an oven.

EXAMPLE 10 Preparation of the Tetrasodium Salt ofa-Carboxymethyloxy-B-Sulfosuccinic Acid Sulfomaleic anhydride (l9.4 gm)is heated to 60C and combined with 76 gm of ethyl glycolate. Afterheating the mixture at 80C for 5% hours, there is added a solution of 45gm of sodium hydroxide dissolved in I35 gm of water and heating iscontinued at 80 for an additional 3 hours. The mixture is then dilutedwith water and passed through a column of a cation exchange resin. Theresulting eluent is then evaporated in vacuo to a low volume and theconcentrate extracted repeatedly with acetone to remove glycolic acidand other impurities. The resulting extracted residue is then dissolvedin water and the pH of the solution adjusted to 8.6 with dilute sodiumhydroxide. Evaporation of the solution in vacuo and drying over P 0gives a residue of the tetrasodium salt ofa-carboxymethyloxy-B-sulfosuccinic acid.

EXAMPLE 1 1 Preparation of Trisodium a-( Z-Hydroxyethylamino)-B-Sulfosuccinate Sulfomaleic anhydride (prepared from a 1]] mole ratioof SO /maleic anhydride by heating the mixture at l00l 10C for 3 hours;active content, 86%), 20.7 gm (0.1 mole), was added to gm of ice. Theresulting solution was kept at l0l 5C and neutralized to pH 8.6 byslowly adding 28.4 gm of 50% sodium hydroxide. Monoethanolamine, 6.1 gm(0.1 mole), was next added slowly and the temperature allowed to rise toroom temperature. After standing overnight, the reaction mixture waspoured into 800 ml of acetone. The solvent was then decanted from theresulting syrupy lower layer and the latter reprecipitated three timesfrom water with fresh acetone. The residue was then dried in adessicator over P 0 to give 38.8 gm of an off-white, granular productcontaining approximately 88% trisodiumoz-(2-hydroxyethylamino)-B-sulfosuccinate by titration with perchloricacid. The structure was confirmed by NMR analysis.

The above method is satisfactory for reacting watersoluble aminocompounds with sulfomaleic anhydride. For water insoluble aminocompounds such as the higher alkyl amines, a mixed solvent system suchas ethanol/water and dioxane/water is used together with temperatures inthe range of 2580C.

Table 2 indicates the reactants and procedure re quired to obtain othera-substituted-B-sulfosuccinate salts having the R and Z moieties setforth in formula 1.

alcohol TABLE 2-continued R Z Example Reactants (Sulfomaleic Anhydride+1 Phenyl 4-8 Phenol Carboxyphenyl l0 Methyl salicylate Alkylphenyl 4-8Alkylphenol mmwwwmmwwwwmmmwwwwmmmmoo QQOOOOOOOOOOOOOOOO b l NNOOObbAb-bbbbbbb Sodium (C -C ulkyl mercaptide Methyl BmercaptopropionateMercaploethanesulfonic acid Methyl 2-mercaptobenzoate" Methylfi-mercuptopropionate" R'O[CH,CH -O),,CH CH SH" Sodium2-hydroxyethylmercaptide Sodium 3-hydroxypropylmcrcaptide Sodiumfi-hydroxyhexylmercaptide Methyl 2-mcrcaptobenzoate "Followed byoxidation to sulfoxide according to Fieser reference. "Followed byoxidation to sulfone according to Ficscr reference.

What is claimed is: 1. An a-substituted-B-sulfosuccinic acid having thegeneral formula:

and the alkali metal, ammonium, or substituted ammonium salt formsthereof wherein the substituted ammonium salts are selected from thegroup consisting of monoethanolammonium, diethanolammonium,triethanolammonium, methylammonium, dimethylammonium trimethylammonium,tetramethylammonium, morpholinium, N-methyl-monoethanolammonium andN-ethylmonoethanolammonium, wherein R is an alkyl group containing l-3Ocarbon atoms.

1. AN A-SUBSTITUTED-B-SULFOSUCCINIC ACID HAVING THE GENERAL FORMULA: 2.The Alpha -substituted- Beta -sulfosuccinates of claim 1 wherein the'''' Alpha ''''-substituent is an alkoxy group containing 9-24 carbonatoms.
 3. The Alpha -substituted- Beta -sulfosuccinates of claim 1wherein the '''' Alpha ''''-substituent is an alkoxy group containing2-8 carbon atoms.
 4. The Alpha -substituted- Beta -sulfosuccinate ofclaim 1 wherein the '''' Alpha ''''-substituent is dodecyloxy.
 5. TheAlpha -substituted- Beta -sulfosuccinate of claim 1 wherein the ''''Alpha ''''-substituent is hexadecyloxy.
 6. The Alpha -substituted- Beta-sulfosuccinate of claim 1 wherein the '''' Alpha ''''-substituent isoctadecyloxy.
 7. The Alpha -alkoxy- Beta -sulfosuccinic acid and thesalt forms thereof of claim 1 wherein the alkoxy group is tetradecyloxy.